Dye composition and method for dyeing hydrophobic fiber with the same

ABSTRACT

In the dyeing of hydrophobic fibers comprising new synthetic fibers, especially those called micronfine fibers, etc., it is difficult to obtain a dyed product having excellent fastness and it is further difficult to obtained a dyed product excellent also in color rendering. The present invention solved the problem as following: 
     A specific dye composition containing a water-insoluble monoazo disperse dye represented by a specific structural formula is used to dye hydrophobic fibers, especially polyester fibers, comprising micronfine fibers, thereby giving a dyed products excellent in fastness balance and color rendering.

TECHNICAL FIELD

The present invention relates to a dye composition and a method fordyeing with the same. More specifically, it relates to a dye compositioncontaining a disperse dye having a specific structure suitable fordyeing hydrophobic fibers, especially polyester fibers, and a method fordyeing hydrophobic fibers with the same.

BACKGROUND OF THE INVENTION

Differentiated products that make use of characteristics provided bysynthetic fibers which are generally termed new synthetic fibers areformed by composite finishing of original yarns having individualproperties, such as micronfine fiber, modified cross-section yarns,blended filament yarns different in shrinkage and the like or by acombination thereof. The texture and the feeling peculiar to syntheticfibers which are not observed in natural fibers, in a silk-like fabric,a thin raised textured fabric (peach skin), a rayon-like fabric and thelike, have been accepted, and they have been rapidly widened on themarket.

However, in the dyeing of these composite materials, there are problemscaused by microfine fibers. For example, the following problems tend tooccur.

(1) A reflected light on a fiber surface is increased to decrease avisual density of a dyed product. Accordingly, in order to obtain thesame surface density of the dyed product as that of the conventionalproduct, a higher color value is required. (A color value is in parallelwith a surface area.)

(2) A dyed product is liable to undergo oxidation and reduction withlight, and a fastness to light of a dyed product is decreased.

(3) Due to (1), an amount of a dye used for a unit area is increased, sothat a fastness to sublimation and a fastness to wetting of a dyedproduct are decreased.

(4) An unevenness (non-level dyeing) of a dyed product occurs owing to adifference in a thickness of composite fibers.

Further, finishing of a ceremonial dress, namely, a formal wear with ablack dye is taken up as one of finishings which have been widelyconducted in recent years. With respect to the dyeing in this field, acolor of a dyed product has been required to be as deep black aspossible, and various studies have been conducted. For example, thereare improvements such as a method for modifying fibers themselves inwhich pores are formed in advance in a surface of a fiber, a finishingmethod in which a resin film having a low refractive index is formed ona surface of a fiber (darkening of a color) and the like, and thedevelopment of a new dye that gives a deep black color. With respect tothe dye in these, it is required that a deep black color is given and acolor deviation which is caused when a light source changes is low, thatis, a so-called color rendering property is low.

In order to solve these problems, not only is it required to use a dyewhich is superior in a fastness and a build-up property, but also it isrequired to develop and use a dye which is excellent in a level dyeingproperty and a solid property of a fabric formed of composite yarnsdifferent in the thickness. Especially, for obtaining a dyed productwith a dark blue or black color, a high build-up property is required,and a color value which is from 2 to 5 times that of a general color isneeded. Besides, in a ceremonial dress, it has been considered good thata color of a dyed product is as deep as possible and a noble black coloris given. Further, a change in color (color deviation) of a dyed productwhich is caused by change of a light source is termed a color renderingproperty. Generally, in a black dyed product, this color deviation tendsto occur. In this instance, a change in color is problematic in manycases under a standard light source A typified by a tungsten lightsource to a color under a standard light source D65 or the like. Thereason is that a relative spectral distribution of a blackbody such as atungsten bulb or the like is extremely different to a standard lightsource D65 or the like, which results in a great change in color. Forexample, spotlights that are often used in hotels, wedding halls or thelike are given by tungsten bulbs in many cases. When the spotlights areilluminated, a phenomenon occurs that a dress which must be dark blackappears extremely reddish.

As a method for improving such a color deviation (color renderingproperty), a method for dyeing with a dye composition containing acompound which has absorption at from 650 to 800 nm is proposed inJP-A-Shou 62-246964, JP-A-Shou 62-246965, JP-A-Hei 5-18955, JP-A-Hei1-28456 and the like. However, the so far developed compounds havingabsorption in the long wavelength (or near infrared) are notsatisfactory with respect to both the effect of improving the colorrendering property and the economics.

The present inventors have assiduously conducted investigations to solvethe problems, and have consequently found that the problems are solvedby conducting dyeing with a dye composition containing a disperse dyehaving a specific structure. This finding has led to the completion ofthe invention.

DISCLOSURE OF THE INVENTION

That is, the invention is:

(1) A dye composition containing a dye represented by formula (1) and adye represented by formula (2). ##STR1## wherein X₁ represents achlorine atom or a bromine atom, and R₁ represents a methyl group or anethyl group.

(2) The dye composition recited in the (1), wherein the dye representedby formula (1) is contained in an amount of from 40 to 95% by weight,and the dye represented by formula (2) in an amount of from 60 to 5% byweight.

(3) The dye composition recited in the (1), which contains the dyerepresented by formula (1), the dye represented by formula (2), and adye represented by formula (3) ##STR2## wherein Y₁ and Z₁, independentlyfrom each other, represent a chlorine atom or a bromine atom, and R₂represents a methyl group or a phenyl group.

(4) The dye composition recited in the (3), wherein the dye representedby formula (1) is contained in an amount of from 40 to 90% by weight,the dye represented by formula (2) in an amount of from 60 to 5% byweight, and the dye represented by formula (3) in an amount of from 5 to60% by weight.

(5) The dye composition of the (1) or (3), which contains, in additionto the dye represented by formula (1), the dye represented by formula(2) and the dye represented by formula (3), a dye represented by formula(4) ##STR3## wherein X₂ represents an oxygen atom or an imino group, andR₃ represents an alkoxyalkyl group, an alkoxyalkoxyalkyl group, analkoxycarbonylalkyl group or an alkyl group which may be branched,provided an alkyl group and an alkoxy group are groups having from 1 to4 carbon atoms.

(6) The dye composition, wherein the dye represented by formula(1) iscontained in an amount of from 40 to 90% by weight, the dye representedby formula (2) in an amount of from 60 to 5% by weight, the dyerepresented by formula (3) in an amount of from 2 to 70% by weight, andthe dye represented by formula (4) in an amount of from 0.1 to 40% byweight.

(7) A method for dyeing a hydrophobic fiber, characterized by using thedye composition recited in the (1), (2), (3), (4), (5) or (6).

(8) A dyed product which is dyed with the dye composition containing thedye represented by formula (1) or (2).

(9) A dyed product which is dyed with the dye composition containing thedye represented by formula (1), (2) or (3).

(10) A dyed product which is dyed with the dye composition representedby formula (1), (2), (3) or (4).

(11) The dyed product of the (8) to (10), wherein the fastness to light,the fastness to sublimation, the fastness to water and the fastness towashing of the dyed product of the (8) to (10) are all grade 3 orhigher.

(12) The dyed product of the (8) to (11), wherein the fastness to light,the fastness to sublimation, the fastness to water and the fastness towashing of the dyed product of the (8) to (11) are all grade 3 orhigher, and the color rendering property thereof is grade 4 or 5.

(13) The dyed product of the (8) to (12) which is a hydrophobic fiber.

(14) The dyed product of the (13), wherein the hydrophobic fiber is afiber containing micronfine fibers.

BEST MODE FOR CARRYING OUT THE INVENTION

The invention is described in detail below.

As stated above, as fibers become microfine, it is required to increasean amount of a dye for obtaining a dyed product having a high depth ofshade, which invites the decrease in the fastness of the dyed product.Accordingly, a higher build-up property and a higher fastness than asusual is required for a dye to be used. Especially, in a blackish darkblue dyed product, an amount of a dye used is required to be from 2 to 5times that of a dye with a general color. Almost no dye that can satisfya fastness in microfine fibers has been seen. Further, in the dyeing ofa composite material, especially a composite material obtained by usingyarns of different deniers, even though the dyeing amounts of themicrofine yarn side and the regular yarn side are the same, there is aproblem that the unevenness (non-level dyeing) of a dyed product occursowing to the decrease in the visual density of the microfine yarn sidefor the foregoing reason. Accordingly, an endurable high fastness isrequired for the microfine yarn side, and properties for which such amaterial can be dyed uniformly or with the solid color are alsorequired. Further, as a method for obtaining a black dyed product, amethod in which the dyeing is conducted mainly using dark blue dispersedyes represented by formula (1) is common. However, most of these darkblue dyes have the maximum absorption wavelength of from 560 to 620. Asa result, there occurs a phenomenon that the color appears reddish undera light source in which the relative spectral distribution is inclinedto the long wavelength side, such as the tungsten bulb. The inventorshave discovered that the phenomenon that the color appears reddish canbe improved much by using the dye composition containing the dark bluedisperse dye of formula (1) and the dye represented by formula (2), orthe dye composition containing, in addition to these dyes, the dyerepresented by formula(3), and as required, further the blue to greendisperse dye represented by formula (4). When the hydrophobic fiber isdyed using the dye composition of the invention, the dyed product isobtained in which the color rendering property is extremely low, thatis, the color deviation under different light sources is extremely low.

Further, it has been found that a dyed product having an excellent leveldyeing property of a composite material of yarns of different deniersand a fastness which is by far superior to that of a conventionalproduct is obtained by using a dye composition containing the dark blueand purple dyes represented by formulas (1) and (2), the orange dyerepresented by formula (3) and the specific blue to green dyerepresented by formula (4). This finding has led to the completion ofthe invention. When the composite material is dyed using the dyecomposition of the invention, a black dyed product which has quite a lowunevenness (non-level dyeing) on the surface of the dyed product, whichis extremely good in the fastnesses to light, sublimation and wetting,which is deep and which is excellent in the color rendering property isobtained.

The dye composition of the invention is prepared by containing the dyerepresented by formula (1) in an amount of preferably from 40 to 95% byweight, more preferably from 50 to 90% by weight, the dye represented byformula (2) in an amount of preferably from 60 to 5% by weight, morepreferably from 50 to 10% by weight, the dye represented by formula (3)in an amount of preferably from 2 to 70% by weight, more preferably from5 to 60% by weight, and the dye represented by formula (4) in an amountof preferably from 0.1 to 40% by weight, more preferably from 0.2 to 30%by weight.

And with respect to the dye represented by formula (1) and the dyerepresented by formula (2) in the dye composition of the invention, itis preferable that the dye represented by formula (1) is contained in anamount of from 40 to 95% by weight and the dye represented by formula(2) in an amount of from 60 to 5% by weight. Further, when the dyerepresented by formula (1), the dye represented by formula (2) and thedye represented by formula (3) are contained in the dye composition ofthe invention, it is preferable that the dye represented by formula (1)is contained in an amount of from 40 to 90% by weight, the dyerepresented by formula (2) in an amount of from 60 to 5% by weight andthe dye represented by formula (3) in an amount of from 5 to 60% byweight. Still further, when the dye represented by formula (1), the dyerepresented by formula (2), the dye represented by formula (3) and thedye represented by formula (4) are contained in the dye composition ofthe invention, it is preferable that the dye represented by formula (1)is contained in an amount of from 40 to 90% by weight, the dyerepresented by formula (2) in an amount of from 60 to 5% by weight, thedye represented by formula (3) in an amount of from 2 to 70% by weightand the dye represented by formula (4) in an amount of from 0.1 to 40%by weight.

Incidentally, examples of the group represented by R₃ in formula (4)include the following. Examples of the alkoxyalkyl group having from 1to 4 carbon atoms include a methoxypropyl group, an ethoxypropyl group,a propoxypropyl group, a butoxypropoxy group, a methoxyisopropyl group,an ethoxyisopropyl group, a methoxyethyl group, a methoxybutyl group, amethoxyisobutyl group, a butoxymethyl group and the like. A (C1-C2)alkoxypropyl or (C1-C2) alkoxyisopropyl group is preferable. Examples ofthe alkoxyalkoxyalkyl group include a methoxymethoxypropyl group, amethoxyethoxypropyl group, a methoxypropoxypropyl group, amethoxybutoxypropyl group, a methoxymethoxyisopropyl group, amethoxyethoxyisopropoxy group, an ethoxymethoxyethyl group, anethoxymethoxybutyl group, a methoxymethoxyisobutyl group, amethoxybutoxymethyl group and the like. Examples of thealkoxycarbonylalkyl group include a methoxycarbonylpropyl group, anethoxycarbonylpropyl group, a propoxycarbonylpropyl group, abutoxycarbonylpropoxy group, a methoxycarbonylisopropyl group, anethoxycarbonylisopropyl group, a methoxycarbonylethyl group, amethoxycarbonylbutyl group, a methoxycarbonylisobutyl group, abutoxycarbonylmethyl group and the like. Examples of the alkyl groupinclude a methyl group, an ethyl group, a propyl group, an isopropylgroup, a butyl group, an isobutyl group and the like. Further, dispersedyes other than those of formulas (1), (2), (3) and (4) may be addedaccording to a desired hue.

As a specific example of the disperse dye represented by formula (1),which is used in the invention, a compound of formula (1) in which whenX₁ is Cl and R₁ is a methyl group or an ethyl group or a compound offormula (1) in which when X₁ is Br and R₁ is a methyl group or an ethylgroup is mentioned. When preferable examples are represented bystructural formulas, a compound of the following formula (5), (6) or (7)and the like are mentioned. ##STR4## A mixture thereof is alsoavailable.

Further, as specific examples of the disperse dye represented by formula(2), a compound of the following formula (8) or (9) and the like arementioned. ##STR5## A mixture thereof is also available.

As a specific example of the disperse dye represented by formula (3), acompound in which Y₁ and Z₁ are chlorine atoms and R₂ is a methyl groupor a phenyl group or a compound in which Y₁ and Z₁ are bromine atoms andR₂ is a methyl group or a phenyl group is mentioned. When preferableexamples are represented by structural formulas, a compound of thefollowing formula (10), (11) or (12) and the like are mentioned.##STR6## A mixture thereof is also available.

Further, as a preferable example of the disperse dye represented byformula (4), a compound in which X₂ is an oxygen atom or an imino groupand R, is a (C1-C2) alkoxypropyl or (C1-C2) alkoxyisopropyl group can bementioned. As specific examples thereof, a compound of the followingformula (13), (14), (15) or (16) and the like are mentioned. ##STR7## Amixture thereof is also available.

As dyes which are added according to a desired hue other than the dyesrepresented by formulas (1), (2), (3) and (4), disperse dyes such as ayellow dye, an orange dye, red to purple dyes and the like arementioned, and these may be added unless qualities of the dyecomposition of the invention are impaired. As one of these dyes, a reddye represented by formula (22) ##STR8## wherein Y₃ and Z₂,independently from each other, represent a nitro group or a halogen atomsuch as a chlorine atom, a bromine atom or the like, and R₆ and R₇,independently from each other, represent a hydrogen atom or a loweralkyl group having from 1 to 4 carbon atoms, such as a methyl group, anethyl group or the like.

It is preferable that this dye is added when a black dye composition isobtained using the dye composition of the invention.

The powder of each dye(no dispersed dye) which is used in the inventionis prepared in the following manner. The powder of the dye representedby formula (1) is a dye known from JP-B-Shou 39-14989 and the like or adisperse dye similar thereto. The powder of the dye represented byformula (2) is a dye known from JP-B-Shou 62-6592 and the like or adisperse dye similar thereto. The powder of the dye represented byformula (3) is a dye known from JP-B-Shou 36-16039 and the like or adisperse dye similar thereto. The powder of the dye represented byformula (4) is a dye known from JP-B-Shou 30-3384, JP-B-Shou 39-14992,JP-B-Shou 41-4872 and the like or a disperse dye similar thereto. Thesecan easily be produced by the methods described therein or by thesimilar methods.

When the hydrophobic fiber is dyed with the dye compositions of theinvention, these dye compositions are used in the dyeing in a statewhere they are wet pulverized and finely dispersed along with anordinary dispersant. For example, an anionic dispersant such as aformalin condensate of naphthalenesulfonic acid, a formalin condensateof an alkylnaphthalenesulfonic acid, a formalin condensate ofcresolsulfonic acid, lignin sulfonic acid or the like, a nonionicdispersant such as a block copolymer of ethylene oxide and propyleneoxide, an ethylene oxide adduct of an alkylphenol, an ethylene oxideadduct of polystyrene phenol or the like, or a mixture of these anionicdispersants and nonionic dispersants (the dispersant is ordinarily usedat a weight ratio of from 1 to 5 times relative to the powder) and asmall amount of water are added to each of the powders of the dyes offormulas (1), (2), (3) and (4) or a mixture of these dye powders. Theresulting blend is wet pulverized well usually to a size of from 0.2 to1μ using a mixing and grinding machine, a sand mill, a sand grinder orthe like. The powder is subjected to the dyeing as such, as a paste, oras a finely divided dye of a dry product by being dried through spraydrying or the like. When the dyes of formulas (1), (2), (3) and (4) areseparately pulverized by the above-mentioned method, the finely divideddyes are mixed in advance or mixed in providing a dye bath to preparethe dye bath, and subjected to the dyeing.

Further, some types of existing disperse dyes can be used, besides thedyes represented by formulas (1), (2), (3) and (4) which are used in theinvention, in order to adjust a hue to a desired one or further improvethe fastness and the dyeability. At that time as well, the powders ofthe dyes may be mixed in advance and then pulverized, or the respectivedyes are finely dispersed, then blended and subjected to the dyeing.

Specific examples of the hydrophobic fiber which can be dyed by themethod of the invention include a polyester (PET) fiber, a polyamidefiber, a diacetate fiber, a triacetate fiber, and a blended productthereof. It may be a blended product with a regenerated fiber such as arayon or the like, or a natural fiber such as cotton, silk, wool or thelike. The thickness of the hydrophobic fiber is preferably between 0.1and 10 d (denier). Especially, a fiber of from 0.1 to 1.0 d is called amicronfine fiber.

When the hydrophobic fiber is dyed using the dye composition of theinvention, it is advantageous that the fiber is dyed in an aqueoussolvent in which the dye is dipped at 105° C. or higher, preferably atfrom 110 to 140° C. under increased pressure. Further, it is alsopossible to conduct the dyeing in the presence of a carrier such aso-phenylphenol, chlorobenzene or the like at a relatively hightemperature, for example, at a boiling temperature of a dye bath.Alternatively, it is also possible to conduct the dyeing by a so-calledthermosol process in which the dye dispersion is padded on a fabric, andthe resulting fabric is subjected to a dry heat treatment at from 150 to230° C. for from 30 seconds to 1 minute.

Meanwhile, the dyeing may be conducted by a printing method in which aprinting paste is prepared along with the dye composition of theinvention and a natural paste (for example, locust bean gum or guargum), a finish paste (for example, a cellulose derivative such ascarboxymethyl cellulose or the like, or a finish locust bean gum), asynthetic paste (for example, polyvinyl alcohol or polyvinyl acetate),and a fabric is printed therewith, and then subjected to a steaming orthermosol treatment Further, the dyeing may be conducted by an ink jetprinting method in which an ink is prepared by adding a non-drying agentsuch as glycerol, diethylene glycol or the like to the dye compositionof the invention, a fabric to which a paste or the like has been appliedthrough padding or the like is printed therewith using an ink jet-typeprinter, and the resulting fabric is then subjected to a steaming orthermosol treatment. When the dyeing is conducted using the dyecomposition of the invention, the amount of the dye composition used isoptional. In the preferred embodiment, in case of, for example, a fiberof 3 denier, it is between 2 to 10% o.w.f. (based on the weight of thefiber).

In the above-obtained dyed product of the invention, the fastness tolight, the fastness to sublimation, the fastness to water and thefastness to washing are grade 3 or higher, and the color renderingproperty is grade 4 or 5. Thus, it exhibits excellent properties withrespect to the fastnesses and the color rendering property.

When the dyed product in the invention is a hydrophobic fiber, morepreferably a polyester fiber and a polyacetate fiber and these fibersare fibers containing micronfine fibers, the outstanding effects areexhibited. However, the dyed product of the invention sometimes includesalso a dyed product in a film, a molded product or the like other thanthe fiber. These dyed products may be obtained by usual methods used bypractitioner having an ordinary skill in the art for dyeing a product tobe dyed, such as, a dyeing method in a dye bath, an integral coloringmethod, a coating method and the like, as required.

The effects of the invention are described by referring to Tables 1 and2.

Table 1 indicates the results of the dyeing with the dye compositions ofthe invention (compositions in Examples 1 to 10 to be described later)and comparative dye compositions (compositions in Comparative Examples 1to 3 to be described later).

                  TABLE 1                                                         ______________________________________                                        Comparison on fastnesses of a micronfine fiber (0.3 d PET) (*1)                       Light (*2)                                                                             Sublimation (*3)                                                                          Water (*4)                                                                           Washing (*5)                              ______________________________________                                        Example 1                                                                             ∘                                                                          ∘                                                                             ∘                                                                        ∘                               Example 2 ∘ ∘ ∘ ∘                                                Example 3 ∘ ∘                                         ∘ ∘                Example 4 ∘ ∘ ∘ ∘                                                Example 5 ∘ ∘                                         ∘ ∘                Example 6 ∘ ∘ ∘ ∘                                                Example 7 ∘ ∘                                         ∘ ∘                Example 8 ∘ ∘ ∘ ∘                                                Example 9 ∘ ∘                                         ∘ ∘                Example 10 ∘ ∘ ∘ ∘                                               Comparative Δ x ∘                                          Δ                                     Example 1                                                                     Comparative Δ x ∘ Δ                                   Example 2                                                                     Comparative Δ x ∘ Δ                                   Example 3                                                                   ______________________________________                                         (*1) A fabric (5.0 g) of a polyester microfine fiber of 0.3 denier was        subjected to exhaustion dyeing under such dyeing conditions that each of      the disperse dye compositions obtained in Examples 1 to 10 and Comparativ     Examples 1 to 3 was 20% (15% in Examples 1 to 10 and Comparative Example      1) o.w.f. (based on the weight of the fiber), the bath ratio 30:1, the pH     4.5, the temperature 130° C. and the time 60 minutes. The resultin     dyed fabrics were subjected to the following fastness tests.                  (*2) Test method for fastness to light: according to JIS L0842 (carbon ar     lamp). The degree of the fading in color practical standard, was rated as     ⊚, grade 2 to 3 as Δ, and grade less than 2 as x.        (*3) Test method for fastness to sublimination: according to JIS L0879 B      sublimination test (180° C., 30 seconds).                              The degree of staining on a polyester white fabric was evaluated using th     JIS staining gray scale. Grade 3 or higher, a practical standard, was         rated as ⊚, grade 2 to 3 as Δ, and grade less than 2     as x.                                                                         (*4) Test method for fastness to water: A dyed fabric was heat set at         180° C. for 30 seconds, and the test was then conducted according      to the JIS L0846 water test A method. The degree of staining on a nylon       white fabric was evaluated using the JIS staining gray scale. Grade 3 or      higher, a practical standard, was rated as ⊚, grade 2 to 3     as Δ, and grade less than 2 as x.                                       (*5) Test method for fastness to washing: AATCC Test Method 61 IIA. The       degree of staining on nylon was evaluated with the JIS staining gray          scale. Grade 3 or higher, a practical standard, was rated as                  ⊚, garde 2 to 3 as Δ, and grade less than 2 as x.   

As shown in Table 1, it is found that the dyed product obtained with thedye composition of the invention is a microfine polyester of 0.3 denierand meets the practical levels with respect to the fastnesses to light,sublimation and wetting (water, washing), and the balance of thefastnesses is be very good. In Comparative Examples, some of thefastnesses to light, sublimation and wetting are found to beunsatisfactory.

Thus, the use of the dye composition of the invention can satisfy thefastnesses in the micronfine fiber which could not be satisfactory inthe conventional dyeing method, and the dyed product which can fullysatisfy the practical levels can be obtained.

Table 2 below show the results of conducting the test for the colorrendering property using black dyed products obtained by conducting thedyeing with the dye compositions containing the dyes represented byformulas (1), (2), (3) and (4) as described in Invention Examples 7 to10.

Table 2 below reveals that the dye compositions in Examples 7, 8, 9 and10 give the dyed product quite a low color rendering property, namelyquite a low color deviation under different light sources. Further, thecolor rendering property is found to be quite low in the dyed productafter the deep dyeing.

                  TABLE 2                                                         ______________________________________                                        Test for color rendering property (*6)                                          Degree of deviation in color under two different light sources                Dye composition    untreated                                                                              after deep dyeing (*7)                          ______________________________________                                        Dye composition in Example 7                                                                   4-5      4-5                                                   Dye composition in Example 8 4-5 4-5                                          Dye composition in Example 9 4-5 4-5                                          Dye composition in Example 10 4-5 4-5                                       ______________________________________                                         (*6) Dyeing method and test method for color rendering property: Three        types of dye baths were prepared by adding pure water which had been          adjustedto pH 4.5 to 10 parts by weight of the dye compositions obtained      in Examples 7 to 10 to adjust the amount to 3,000 parts by weight. One        hundred parts by weight of a polyester tropical fabric were dipped            therein, and dyed at 130° C. for 60 minutes. Then, the dyed produc     was reductively washed at 80° C. for 10 minutes in a bath obtained     by adding 6 parts by weight of 45% sodium hydroxide, 6 parts by weight of     hydrosulfite and 3 parts by weight of Sunmorl RC700 (supplied by Nikka        Kagaku K.K., anionic surfactant) to pure water to adjust the total amount     to 3,000 parts by weight. The resulting fabric was washed with water, and     dried to obtained a black dyed fabric. The thusobtained dyed fabrics were     subjected to the test for the color rendering property. In the test for       the color rendering property, the degree of the deviation in color under      commercial tungsten lamp (National Lamp PRF500 W, supplied by Matsushite      Electric Industrial Co., Ltd.) of a color temperature 5500K was visually      evaluated using the JIS gray scale evaluation grades deviation in color       with a color under illumination of a D65 standard light source prescribed     by JIS as a standard.                                                         (*7) Deep dyeing treatment and test for color rendering property: Each of     the dyed fabrics obtained in the (*6) was padded with a solution              containing 40 parts by weight of Schwat TR420 (supplied by Kao                Corporation, special resin finishing agent) and adjusted to a pH of 4 in      total amount of 1,000 parts by weight, intermediately dried, and then         subjected to a dry heat treatment at 180° C. for 2 minutes. The        resulting fabric was subjected to the same test for the color rendering       property as in the (*6).                                                 

The invention is illustrated more specifically by referring to thefollowing Examples. In Examples, parts and % are parts by weight and %by weight respectively.

EXAMPLE 1

Sixteen parts of the powder of the dye represented by formula (5) and 7parts of the powder of the dye represented by formula (8) werepulverized (dispersed) along with 20 parts of Demol N (trade name; ananionic dispersant, supplied by Kao Corporation) and 57 parts of purewater using a sand grinder to obtain a liquid dye composition of theinvention. A dye bath was prepared by adding pure water which had beenadjusted to pH 4.5 to 15 parts of this dye composition to adjust theamount to 3,000 parts. One hundred parts of a fabric of a polyestermicrofine fiber of 0.3 denier were dipped therein, and dyed at 130° C.for 60 minutes. Then, the dyed fabric was reductively washed at 80° C.for 10 minutes in a bath prepared by adding water to 6 parts of 45%sodium hydroxide, 6 parts of hydrosulfite and 3 parts of Sunmor RC-700(trade name; an anionic surfactant, supplied by Nikka Kagaku K.K.) toadjust the total amount to 3,000 parts. The fabric was washed withwater, and dried to obtain a dark blue dyed fabric. The thus-obtaineddyed fabric was quite excellent in all of fastnesses to light,sublimation and wetting.

EXAMPLE 2

The powder (14.7 parts) of the dye represented by formula (6) and 7.1parts of the powder of the dye represented by formula (9) werepulverized (dispersed) along with 20 parts of Demol N and 58.2 parts ofpure water using a sand grinder to obtain a liquid dye composition ofthe invention. A dye bath was prepared by adding pure water which hadbeen adjusted to pH 4.5 to 15 parts of this dye composition to adjustthe amount to 3,000 parts. One hundred parts of a fabric of a polyestermicrofine fiber of 0.3 denier were dipped therein, and dyed at 130° C.for 60 minutes. Then, the dyed fabric was reductively washed at 80° C.for 10 minutes in a bath prepared by adding water to 6 parts of 45%sodium hydroxide, 6 parts of hydrosulfite and 3 parts of Sunmor RC-700to adjust the total amount to 3,000 parts. The fabric was washed withwater, and dried to obtain a dark blue dyed fabric. The thus-obtaineddyed fabric was quite excellent in all of fastnesses to light,sublimation, water and washing.

EXAMPLE 3

The powder (7.7 parts) of the dye represented by formula (5), 4 parts ofthe powder of the dye represented by formula (8) and 13 parts of thepowder of the dye represented by formula (10) were pulverized(dispersed) along with 20 parts of Demol N and 55.3 parts of pure waterusing a sand grinder to obtain a liquid dye composition. A dye bath wasprepared by adding pure water which had been adjusted to pH 4.5 to 20parts of this dye composition to adjust the amount to 3,000 parts. Onehundred parts of a fabric of a polyester microfine fiber having 0.3denier were dipped therein, and dyed at 130° C. for 60 minutes. Then,the dyed fabric was reductively washed at 80° C. for 10 minutes in abath prepared by adding water to 6 parts of 45% sodium hydroxide, 6parts of hydrosulfite and 3 parts of Sunmor RC-700 to adjust the totalamount to 3,000 parts. The fabric was washed with water, and dried toobtain a dark blue dyed fabric. The thus-obtained dyed fabric was quiteexcellent in all of fastnesses to light, sublimation and wetting.

EXAMPLE 4

The powder (8.1 parts) of the dye represented by formula (5), 3.5 partsof the powder of the dye represented by formula (8), 13 parts of thepowder of the dye represented by formula (10) and 1.2 parts of a red dyerepresented by the following formula (17) were pulverized (dispersed) asin Example 3 to obtain a liquid dye composition of the invention. Thiswas dyed similar to Example 3 to obtain a black dyed fabric. Theresulting dyed fabric was quite excellent in all of fastnesses to light,sublimation and wetting. ##STR9##

EXAMPLE 5

Eight parts of the powder of the dye represented by formula (7), 4 partsof the powder of the dye represented by formula (9), 13 parts of thepowder of the dye represented by formula (11) and 1.5 parts of the reddye represented by formula (17) were pulverized (dispersed) as inExample 3 to obtain a liquid dye composition of the invention. This wasdyed similar to Example 3 to obtain a black dyed fabric. The resultingdyed fabric was quite excellent in all of fastnesses to light,sublimation and wetting.

EXAMPLE 6

Eight parts of the powder of the dye represented by formula (7), 3.6parts of the powder of the dye represented by formula (9), 12 parts ofthe powder of the dye represented by formula (12) and 1.2 parts of a reddye represented by the following formula (18) were pulverized(dispersed) as in Example 3 to obtain a liquid dye composition of theinvention. This was dyed similar to Example 3 to obtain a black dyedfabric. The resulting dyed fabric was quite excellent in all offastnesses to light, sublimation and wetting. ##STR10##

EXAMPLE 7

The powder (7.7 parts) of the dye represented by formula (5), 4 parts ofthe powder of the dye represented by formula (8), 13 parts of the powderof the dye represented by formula (9) and 1.2 parts of the powder of thedye represented by formula (13) were pulverized (dispersed) as inExample 3 to obtain a liquid dye composition of the invention. This wasdyed similar to Example 3 to obtain a black dyed fabric. The resultingdyed fabric was quite excellent in all of fastnesses to light,sublimation and wetting and color rendering property.

EXAMPLE 8

The powder (8.1 parts) of the dye represented by formula (5), 3.5 partsof the powder of the dye represented by formula (8), 13 parts of thepowder of the dye represented by formula (10) and 1.1 parts of thepowder of the dye represented by formula (14) were pulverized(dispersed) as in Example 3 to obtain a liquid dye composition of theinvention. This was dyed similar to Example 3 to obtain a black dyedfabric. The resulting dyed fabric was quite excellent in all offastnesses to light, sublimation and wetting and color renderingproperty.

EXAMPLE 9

Eight parts of the powder of the dye represented by formula (7), 4.0parts of the powder of the dye represented by formula (9), 13 parts ofthe powder of the dye represented by formula (13) and 1. 0 part of thepowder of the dye represented by formula (15) were pulverized(dispersed) as in Example 3 to obtain a liquid dye composition of theinvention. This was dyed similar to Example 3 to obtain a black dyedfabric. The resulting dyed fabric was quite excellent in all offastnesses to light, sublimation and wetting and color renderingproperty.

EXAMPLE 10

Eight parts of the powder of the dye represented by formula (7), 3.6parts of the powder of the dye represented by formula (9), 12 parts ofthe powder of the dye represented by formula (12) and 1.0 part of thepowder of the dye represented by formula (16) were pulverized(dispersed) as in Example 3 to obtain a liquid dye composition. This wasdyed similar to Example 3 to obtain a black dyed fabric. The resultingdyed fabric was quite excellent in all of fastnesses to light,sublimation and wetting and color rendering property.

COMPARATIVE EXAMPLE 1 to 3

Liquid dye compositions for comparison with the dye compositions of theinvention were prepared in the same manner as in Examples except that adye represented by the following formula (19) was used instead of thedark blue to purple dyes of formulas (1) and (2), a dye represented bythe following formula (20) instead of the orange dye of formula (3) anda dye represented by the following formula (21) instead of the blue togreen dye of formula (4). ##STR11## At that time, as dye compositionsused for blending, disperse dyes prepared in a usual manner in whichsubstituents X₃, Y₂, R₄ and R₅ in formulas (19), (20) and (21) were asshown in Table 3 below were used in amounts shown in Table 4 below. Inthe table, the amounts of the powder of the dye, the dye for coloradjustment, the dispersant and water were indicated in terms of parts byweight.

                  TABLE 3                                                         ______________________________________                                        X.sub.3, Y.sub.2, R.sub.4 and R.sub.5 in formulas (19), (20) and (21)                   For-                                                                                                       mula X                                                                       .sub.3 Y.sub.2 R.sub.4 R.sub.5          ______________________________________                                        Example 1                                                                             a     19     Br   OMe  C.sub.2 H.sub.4 OCOMe                                                                  C.sub.2 H.sub.4 OCOMe                    b 19 Br H Et Et                                                              Example 2 a 19 Br OEt C.sub.2 H.sub.4 OCOMe C.sub.2 H.sub.4 OCOMe                                                     b 19 Cl H Et Et                       Example 3 a 19 Br OMe C.sub.2 H.sub.4 OCOMe C.sub.2 H.sub.4 OCOMe                                                     b 19 Br H Et Et                        c 20 Cl Cl C.sub.2 H.sub.4 OCOMe --                                          Example 4 a 19 Br OMe C.sub.2 H.sub.4 OCOMe C.sub.2 H.sub.4 OCOMe                                                     b 19 Br H Et Et                        c 20 Cl Cl C.sub.2 H.sub.4 OCOMe --                                          Example 5 a 19 Cl OMe C.sub.2 H.sub.4 OCOMe C.sub.2 H.sub.4 OCOMe                                                     b 19 Cl H Et Et                        c 20 Br Br C.sub.2 H.sub.4 OCOMe --                                          Example 6 a 19 Cl OMe C.sub.2 H.sub.4 OCOMe C.sub.2 H.sub.4 OCOMe                                                     b 19 Cl H Et Et                        c 20 Cl Cl C.sub.2 H.sub.4 OCOPh --                                          Example 7 a 19 Br OMe C.sub.2 H.sub.4 OCOMe C.sub.2 H.sub.4 OCOMe                                                     b 19 Br H Et Et                        c 20 Cl Cl C.sub.2 H.sub.4 OCOMe --                                           d 21 O -- C.sub.3 H.sub.6 OMe --                                             Example 8 a 19 Br OMe C.sub.2 H.sub.4 OCOMe C.sub.2 H.sub.4 OCOMe                                                     b 19 Br H Et Et                        c 20 Cl C C.sub.2 H.sub.4 OCOMe --                                            d 21 O -- C.sub.3 H.sub.6 OEt --                                             Example 9 a 19 Cl OMe C.sub.2 H.sub.4 OCOMe C.sub.2 H.sub.4 OCOMe                                                     b 19 Cl H Et Et                        c 20 Br Br C.sub.2 H.sub.4 OCOMe --                                           d 21 NH -- C.sub.3 H.sub.6 OMe --                                            Example 10 a 19 Cl OMe C.sub.2 H.sub.4 OCOMe C.sub.2 H.sub.4 OCOMe                                                    b 19 Cl H Et Et                        c 20 Cl Cl C.sub.2 H.sub.4 OCOMe --                                           d 21 NH -- C.sub.2 H.sub.4 (OMe)Me --                                        Comparative a 19 Br OMe Et Et                                                 Example 1 b 19 Br H Et Et                                                     Comparative a 19 Br OMe Et Et                                                 Example 2 b 19 Br H Et Et                                                      c 20 Cl Cl C.sub.2 H.sub.4 OCOMe --                                          Comparative a 19 Br OMe Et Et                                                 Example 3 b 19 Br H Et Et                                                      c 20 Cl Cl C.sub.2 H.sub.4 OCOMe --                                        ______________________________________                                         *8) In Table 3 above, Me means a methyl group, Et an ethyl group, and Ph      phenyl group.                                                            

                  TABLE 4                                                         ______________________________________                                        Formulation of a dye composition                                                         Amount of                                                            an powder Dye for color                                                       of a dye adjustment Dispersant Pure water                                   ______________________________________                                        Example 1                                                                             a      16.0     --       20     57.0                                     b  7.0                                                                       Example 2 a 14.7 -- 20 58.2                                                    b  7.1                                                                       Example 3 a  7.7 -- 20 55.3                                                    b  4.0                                                                        c 13.0                                                                       Example 4 a  8.1 1.2 20 54.2                                                   b  3.5 (*9)                                                                   c 13.0                                                                       Example 5 a  8.0 1.5 20 53.5                                                   b  4.0 (*9)                                                                   c 13.0                                                                       Examplee a  8.0 1.2 20 55.2                                                    b  3.6 (*10)                                                                  c 12.0                                                                       Example 7 a  7.7 -- 20 54.1                                                    b  4.0                                                                        c 13.0                                                                        d  1.2                                                                       Example 8 a  8.1 -- 20 54.3                                                    b  3.5                                                                        c 13.0                                                                        d  1.1                                                                       Example 9 a  8.0 -- 20 54.0                                                    b  4.0                                                                        c 13.0                                                                        d  1.0                                                                       Example 10 a  8.0 -- 20 55.4                                                   b  3.6                                                                        c 12.0                                                                        d  1.0                                                                       Comparative a 15.4 -- 20 58.0                                                 Example 1 b  6.6                                                              Comparative a  6.0 -- 20 58.0                                                 Example 2 b  3.5                                                               c 12.5                                                                       Comparative a  8.0 1.5 20 55.3                                                Example 3 b  3.4 (*9)                                                          c 11.8                                                                     ______________________________________                                         *9) using the red dye represented by formula (17).                       

INDUSTRIAL APPLICABILITY

A dyed product which is quite good in balance of fastnesses to light,sublimation and wetting and which is excellent in color renderingproperty can be obtained by using the dye composition of the inventionwhen dyeing a composite material of a hydrophobic fiber containing amicrofine synthetic fiber called a micronfine fiber or the like. Thus,it is extremely valuable in the dyeing industry.

What is claimed is:
 1. A black dye composition containing a dyerepresented by formula (1): ##STR12## a dye represented by formula (2):##STR13## wherein X₁ represents a chlorine atom or a bromine atom and R₁represents a methyl group or an ethyl group, and a dye represented byformula (3): ##STR14## wherein Y₁ and Z₁, independently from each other,represent a chlorine atom or a bromine atom, and R₂ represents a methylgroup or a phenyl group.
 2. The black dye composition recited in claim1, wherein the dye represented by formula (1) is contained in an amountof from 40 to 90% by weight, the dye represented by formula (2) in anamount of from 60 to 5% by weight, and the dye represented by formula(3) in an amount of from 5 to 60% by weight.
 3. A black dye compositioncontaining a dye represented by formula (1): ##STR15## a dye representedby formula (2): ##STR16## wherein X₁ represents a chlorine atom or abromine atom and R₁ represents a methyl group or an ethyl group, a dyerepresented by formula (3): ##STR17## wherein Y₁ and Z₁, independentlyfrom each other, represent a chlorine atom or a bromine atom, and R₂represents a methyl group or a phenyl group, and a dye represented byformula (4): ##STR18## wherein X₂ represents an oxygen atom or an iminogroup, and R₃ represents an alkoxyalkyl group, an alkoxyalkoxyalkylgroup, and alkoxycarbonylalkyl group or an alkyl group which may bebranched, provided an alkyl group and an alkoxy group are groups havingfrom 1 to 4 carbon atoms.
 4. The black dye composition recited in claim3, wherein the dye represented by formula (1) is contained in an amountof from 40 to 90% by weight, the dye represented by formula (2) in anamount of from 60 to 5% by weight, the dye represented by formula (3) inan amount of from 2 to 70% by weight, and the dye represented by formula(4) in an amount of from 0.1 to 40% by weight.
 5. A method for dyeing ahydrophobic fiber, characterized by using the black dye compositionrecited in claim 1, 2, 3 or
 4. 6. A dyed product which is dyed with ablack dye composition containing a dye represented by formula (1):##STR19## a dye represented by formula (2): ##STR20## wherein X₁represents a chlorine atom or a bromine atom, R₁ represents a methylgroup or an ethyl group, and a dye represented by formula (3): ##STR21##wherein Y₁ and Z₁, independently from each other, represent a chlorineatom or a bromine atom, and R₂ represents a methyl group or a phenylgroup.
 7. A dyed product which is dyed with a black dye compositioncontaining a dye represented by formula (1): ##STR22## a dye representedby formula (2): ##STR23## wherein X₁ represents a chlorine atom or abromine atom, R₁ represents a methyl group or an ethyl group, a dyerepresented by formula (3): ##STR24## wherein Y₁ and Z₁, independentlyfrom each other, represent a chlorine atom or a bromine atom, and R₂represents a methyl group or a phenyl group, and a dye represented byformula (4): ##STR25## wherein X₂ represents an oxygen atom or an iminogroup, and R₃ represents an alkoxyalkyl group, an alkoxyalkoxyalkylgroup, and alkoxycarbonylalkyl group or an alkyl group which may bebranched, provided an alkyl group and an alkoxy group are groups havingfrom 1 to 4 carbon atoms.
 8. The dyed product of claim 6 or 7, whereinthe fastness to light, the fastness to sublimation, the fastness towater and the fastness to washing of the dyed product of claim 6 or 7are all grade 3 or higher.
 9. The dyed product of claim 6 or 7, whereinthe color rendering property of the dyed product of claim 6 or 7 isgrade 4 or
 5. 10. The dyed product of claim 6 or 7 which is ahydrophobic fiber.
 11. The dyed product of claim 10, wherein thehydrophobic fiber is a micronfine fiber.
 12. The dyed product of 8,wherein the color rendering property of the dyed product of claim 11 isgrade 4 or
 5. 13. The dyed product of claim 8 which is a hydrophobicfiber.
 14. The dyed product of claim 9 which is a hydrophobic fiber. 15.The dyed product of claim 12 which is a hydrophobic fiber.